Four polyaniline hybrid materials were prepared by liquid-state synthesis method in the presence of dopant which synthesized by transition metal mono-substituted Keggin structure silicotungstate anions α, βi-[SiW11Ga(H2O)O39]4-. The polyaniline hybrid materials were characterized by elemental analysis, IR spectroscopy, fluorescence spectroscopy, scanning electeon microscopy (SEM) and thermo gravimetric analysis, the properties of which such as thermal stability and conducting behavior were studied. It proved that the average diameter was 100nm, the conductivity was 9×10-2s•cm-1 and the flourescence property was better.